i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Review

Hydrogen from biomass e Present scenario and future prospects

Havva Balat*, Elif Krtay
Sila Science & Energy Company, University Mah, Trabzon, Turkey

article info
Article history: Received 22 March 2010 Received in revised form 23 April 2010 Accepted 23 April 2010 Available online 20 May 2010 Keywords: Hydrogen Biomass Production Gasication Future prospects

abstract
Hydrogen is considered in many countries to be an important alternative energy vector and a bridge to a sustainable energy future. Hydrogen is not an energy source. It is not primary energy existing freely in nature. Hydrogen is a secondary form of energy that has to be manufactured like electricity. It is an energy carrier. Hydrogen can be produced from a wide variety of primary energy sources and different production technologies. About half of all the hydrogen as currently produced is obtained from thermo catalytic and gasication processes using natural gas as a starting material, heavy oils and naphtha make up the next largest source, followed by coal. Currently, much research has been focused on sustainable and environmental friendly energy from biomass to replace conventional fossil fuels. Biomass can be considered as the best option and has the largest potential, which meets energy requirements and could insure fuel supply in the future. Biomass and biomass-derived fuels can be used to produce hydrogen sustainably. Biomass gasication offers the earliest and most economical route for the production of renewable hydrogen. 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Petroleum-based fuels became the primary source of energy for transportation needs in the 20th century. This has continued in the beginning of the 21st century with almost all vehicles running. On gasoline, diesel or natural gas [1]. The continued use of fossil fuels to meet the majority of the worlds energy demand is threatened by increasing concentrations of carbon dioxide (CO2) in the atmosphere and concerns over global warming [2]. Moreover, the petroleum is a nite source for fuel that is rapidly becoming scarcer and more expensive. Petroleum-based fuels are limited reserves concentrated in certain regions of the world [3]. Environmental, economical and political concerns are generating a growing interest in biofuels. Biofuels produced from natural oils and fats, which can be used as substitutes for gasoline and

petroleum diesel fuels. In addition to being biodegradable and non-toxic, they are also essentially free of sulfur and aromatics, producing lower exhaust emissions than conventional gasoline and diesel fuel whilst providing similar properties in terms of fuel efciency [4]. The term biofuel is referred to as liquid or gaseous fuels for the transport sector that are predominantly produced from biomass. Large-scale production of biofuels offers an opportunity for certain developing countries to reduce their dependence on oil imports. In developed countries there is a growing trend towards employing modern technologies and efcient bioenergy conversion using a range of biofuels, which are becoming cost-wise competitive with fossil fuels [5]. For this reason, alternate transportation fuels such as bioethanol, biodiesel, and hydrogen will play an important role in the worlds future.

* Corresponding author. Tel.: 90 462 871 3025; fax: 90 462 871 3110. E-mail address: havvabalat@yahoo.com (H. Balat). 0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2010.04.137

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

7417

Hydrogen production is one of the most promising alternative energy technologies. It is not primary energy existing freely in nature. Hydrogen is a secondary form of energy that has to be manufactured like electricity. It is an energy carrier. The majority of the experts consider that hydrogen has a great role to play as an important energy carrier in the future energy sector [6,7]. Hydrogen is clean fuel with no CO2 emissions and can easily be used in fuel cells for generation of electricity. Besides, hydrogen has a high energy yield of 122 kJ/g, which is 2.75 times greater than hydrocarbon fuels [8]. The use of hydrogen as a fuel for transportation and stationary applications is receiving much favorable attention as a technical and policy issue [9]. Hydrogen gas is being explored for use in combustion engines and fuel cell electric vehicles. It is a gas at normal temperatures and pressures, which presents greater transportation and storage hurdles than exist for the liquid fuels [10]. Hydrogen can be stored chemically or physiochemically in various solid and liquid compounds (metal hydrides, carbon nanostructures, alanates, borohydrides, methane, methanol, light hydrocarbons) [11].

Hydrogen can be used as a transportation fuel, whereas neither nuclear nor solar energy can be used directly. It has good properties as a fuel for internal combustion engines in automobiles. Hydrogen can be used as a fuel directly in an internal combustion engine not much different from the engines used with gasoline [19]. Hydrogen has very special properties as a transportation fuel, including a rapid burning speed, a high effective octane number, and no toxicity or ozone-forming potential. It has much wider limits of ammability in air (4%e75% by volume) than methane (5.3%e15% by volume) and gasoline (1%e7.6% by volume) [7].

3.
3.1.

Hydrogen production from biomass

Overview of biomass

2. Current status of hydrogen production and use

Hydrogen can be produced from a wide variety of primary energy sources and different production technologies. Most hydrogen is currently produced from nonrenewable sources such as oil, natural gas, and coal. About half of all the hydrogen as currently produced is obtained from thermo catalytic and gasication processes using natural gas as a starting material, heavy oils and naphtha make up the next largest source, followed by coal [12], and only 4% and 1% is generated from water using electricity and biomass, respectively [13]. In short, fossil fuel-based processes account for 95% of global hydrogen production. The production of hydrogen from fossil fuels causes the coproduction of CO2, which is assumed to be the main responsible for the so-called greenhouse effect. Hydrogen produced through a range of renewable primary energy sources such as wind, biomass, and solar energy is ideal for gradually replacing fossil fuels [14]. Biomass and biomassderived fuels can be used to produce hydrogen sustainably. Using biomass instead of fossil fuels to produce hydrogen reduces the net amount of CO2 released to the atmosphere, since the CO2 released when the biomass is gasied was previously absorbed from the atmosphere and xed by photosynthesis in the growing plants [15]. Current total annual worldwide hydrogen consumption is in the range of 400e500 billion Nm3 [16]. Present utilization of hydrogen is equivalent to 3% of the energy consumption and with a growth rate estimated at 5e10% per year [12]. Only a fraction of this hydrogen is currently used for energy purposes; the bulk serves as a chemical feedstock for petrochemical, food, electronics and metallurgical processing industries. The global market for hydrogen is already greater than US$40 billion per year [17]; including hydrogen used in ammonia production (49%), petroleum rening (37%), methanol production (8%), and miscellaneous smaller-volume uses (6%) [18].

Biomass, mainly in the form of wood, is the oldest form of energy used by humans. Traditionally, biomass has been utilized through direct combustion, and this process is still widely used in many parts of the world. The most important biomass energy sources are wood and wood wastes, agricultural crops and their waste byproducts, municipal solid waste, animal wastes, waste from food processing, and aquatic plants and algae. Energy from biomass fuels is used in the electric utility, lumber and wood products, and pulp and paper industries. Currently, much research has been focused on sustainable and environmental friendly energy from biomass to replace conventional fossil fuels.

3.1.1.

Components of biomass

The chemical structure and major organic components in biomass are extremely important in the development of processes for producing derived fuels and chemicals [19]. The chemical components of lignocellulose can be divided into four major components. They are cellulose, hemicelluloses, lignin and extractives [20]. Generally, the rst three components have high molecular weights and contribute much mass, while the last component is of small molecular size, and available in little quantity [21]. Cellulose hemicellulose contents are more in hardwoods (78.8%) than softwoods (70.3%), but lignin is more in softwoods (29.2%) than hardwoods (21.7%) [22]. Cellulose, which is an abundant component in plants and wood, comes in various forms and a large fraction comes from domestic and industrial wastes [23]. Cellulose is a high molecular weight linear polymer of b-1,4-linked D-glucose units which can appear as a highly crystalline material [24]. Glucose anhydride, which is formed via the removal of water from each glucose, is polymerized into long cellulose chains that contain 5000e10000 glucose units. The basic repeating unit of the cellulose polymer consists of two glucose anhydride units, called a cellobiose unit [25]. Hemicellulose is a mixture of various polymerized monosaccharides such as glucose, mannose, galactose, xylose, arabinose, 4-O-methyl glucuronic acid and galacturonic acid residues [25]. Among the most important sugar of the hemicelluloses component is xylose. In hardwood xylan, the backbone chain consists of xylose units which are linked by b(1,4)-glycosidic bonds and branched by a-(1,2)-glycosidic

7418

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

bonds with 4-O-methyl glucuronic acid groups [21]. Hemicelluloses exhibit lower molecular weights than cellulose. The number of repeating saccharide monomers is only w150, compared to the number in cellulose [25]. Lignin is an aromatic polymer synthesised from phenylpropanoid precursors. The basic chemical phenylpropane units of lignin (primarily syringyl, guaiacyl and p-hydroxy phenol) are bonded together by a set of linkages to form a very complex matrix. This matrix comprises a variety of functional groups, such as hydroxyl, methoxyl and carbonyl, which impart a high polarity to the lignin macromolecule [26].

to be the direct combustion of residues and wastes for electricity generation [38].

3.2.

Biomass feedstocks for hydrogen production

3.1.2.

Importance of biomass

Biomass energy (bioenergy) utilization has gained particular interest in recent years due to the progressive depletion of conventional fossil fuels that calls for an increased use of renewable energy sources [27]. Growing interest in bioenergy is driven by the following facts among others [28]: (i) it contributes to poverty reduction in developing countries, (ii) it meets energy needs at all times, without expensive conversion devices, (iii) it can deliver energy in all forms that people need (liquid and gaseous fuels, heat and electricity), (iv) it is CO2-neutral and can even act as carbon sinks, and (v) it helps to restore unproductive and degraded lands, increasing biodiversity, soil fertility and water retention. Importance of biomass will increase as national energy policy and strategy focuses more heavily on renewable sources and conservation.

The use of renewable biomass as a major feedstock for hydrogen production has received considerable attention in recent years. Hydrogen can be generated from biomass, but this technology urgently needs further development. The production of hydrogen from biomass is already economically competitive today. Hydrogen from biomass has many advantages [39]: (i) independence from oil imports, (ii) net product remains within the country, (iii) stable pricing level, (iv) peace keeping, and (v) the CO2 balance can be improved by around 30%. Two types of biomass feedstock are available to be converted into hydrogen [40]: (i) dedicated bioenergy crops, and (ii) less expensive residues, such as organic waste from regular agricultural farming and wood processing (biomass residues). The list of some biomass material used for hydrogen production is given in Table 1 [41]. In general, biomass from energy crops, such as sweet sorghum, can be used as raw material for hydrogen production [42]. Biomass, especially organic waste, offers an economical, environmental-friendly way for renewable hydrogen production [43].

3.3.

Hydrogen production routes from biomass

3.1.3.

Contribution of biomass in global energy supply

Biomass can be considered as the best option and has the largest potential, which meets energy requirements and could insure fuel supply in the future. Biomass energy resources are potentially the worlds largest and most sustainable energy source, a renewable resource comprising 220 billion oven-dry tons (about 4500 EJ) of annual primary production [29]. About 5% of this energy, or 225 EJ, should cover almost 50% of the worlds total primary energy demand at present [30]. However, total biomass contributed around 10% to meet the 470 EJ world primary energy demand in 2007, though this was mainly in the form of traditional non-commercial biomass [30,31]. The future potential for biomass could reach 150e400 EJ/yr (up to 25% of world primary energy) by 2050 with the use of forest and urban residues, in addition to growing perennial energy crops [31]. Currently, much research has been focused on sustainable and environmental friendly energy from biomass to replace conventional fossil fuels. Biomass can be converted to a number of secondary energy carriers (electricity, gaseous, liquid and solid fuels and heat) using a wide range of conversion routes. The conversion routes to fuels and electricity can be distinguished in thermal, chemical and biochemical conversion routes [32]. There have been developed thermo chemical conversion technologies such as pyrolysis [33], gasication [34], liquefaction [35], and supercritical uid extraction [36] for maximizing liquid yields. Direct combustion is the old way of using biomass. Biomass thermo chemical conversion technologies such as pyrolysis and gasication are certainly not the most important options at present; combustion is responsible for over 97% of the worlds bioenergy production [37]. In industrialized countries, the main biomass processes utilized in the future are expected

The methods available for the hydrogen production from biomass can be divided into two main categories: thermo chemical and biological routes. The major biomass-to-hydrogen pathways are shown in Fig. 1 [44]. Hydrogen can be produced from biorenewable feedstocks via thermo chemical conversion processes such as pyrolysis, gasication, steam gasication, steam reforming of bio-oils, and supercritical water gasication. Biological production of hydrogen can be classied into the following groups: (i) biophotolysis of water using green algae and blue-green algae (cyanobacteria), (ii) photo-fermentation, (iii) dark-fermentation, and (iv) hybrid reactor system. The advantage of the thermo chemical process is that its overall efciency (thermal to hydrogen) is higher (hw52%) and production cost is lower [45]. The yield of hydrogen that can be produced from biomass is relatively low, 16e18% based on dry biomass weight [46]. Hydrogen yields and energy contents,

Table 1 e List of some biomass material used for hydrogen production. Biomass species
Bio-nut shell Olive husk Tea waste Crop straw Black liquor Municipal solid waste Crop grain residue Pulp and paper waste Petroleum basis plastic waste Manure slurry

Main conversion process

Steam gasication Pyrolysis Pyrolysis Pyrolysis Steam gasication Supercritical water extraction Supercritical uid extraction Microbiol fermentation Supercritical uid extraction Microbiol fermentation

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

7419

Table 3 e Hydrogen production from conversion of oil palm shell and physic nut waste. Type biomass/Temperature
Oil palm shell 773 K 973 K 1173 K Physic Nut 773 K 973 K 1173 K Source: Ref. [50].

Gas production (vol.%)

3.56 12.58 33.49 8.22 9.29 11.63

Fig. 1 e Pathways from biomass-to-hydrogen. Source: Ref. [44].

compared, with biomass energy contents obtained from processes with biomass, are shown in Table 2 [47]. In the pyrolysis and gasication processes, water gas shift is used to convert the reformed gas into hydrogen, and pressure swing adsorption is used to purify the product. Comparison with other biomass thermo chemical gasication such as air gasication or steam gasication, the supercritical water gasication can directly deal with the wet biomass without drying, and have high gasication efciency in lower temperature [48]. The major disadvantage of these processes is the decomposition of the biomass feedstock leading to char and tar formation [49]. In order to optimize the process for hydrogen production, a number of efforts have been made by researchers to test hydrogen production from biomass gasication/pyrolysis with various biomass types and at various operating conditions, an example of oil palm shell compared with physic nut waste is listed in Table 3 [50]. Biological hydrogen production processes are found to be more environment friendly and less energy intensive as compared to thermo chemical and electrochemical processes [51]. Researchers have started to investigate hydrogen production with anaerobic bacteria since 1980s [52]. Biological production of hydrogen (biohydrogen) as a byproduct of microorganism metabolism is an exciting new area of

technology development that offers the potential production of usable hydrogen from a variety of renewable resources [53]. There are three types of microorganisms of biohydrogen generation: cyano-bacteria, anaerobic bacteria, and fermentative bacteria. A promising method is the biological production of hydrogen by fermentation. The production of hydrogen from biomass by fermentation is one of the routes that can contribute to a future sustainable hydrogen economy. The amount of hydrogen produced from glucose is affected by fermentation pathways and liquid end-products [54]. Butyric acid and acetic acid constituted more than 80% of total endproducts [55]. Theoretically, 4 mol of H2 are produced from 1 mol of glucose in acetate type fermentation, however only 2 mol of H2 produced when butyrate is the main fermentation product. To date, many studies have been done on fermentative hydrogen production from pure sugars and from feedstocks, such as byproducts from the agricultural and food industry, municipal waste, or wastewaters [56]. Anaerobic digestion of solid organic waste, including municipal and agricultural wastes and wastewater sludge, is one such renewable source for H2 production. However, continual H2 production using this process has limitations one of which is the low yields of hydrogen currently realized from the fermentation of even the simplest sugars [57]. A combination of dark and photo-fermentation in a two-stage hybrid system can improve the overall yield of hydrogen [58]. Anaerobic bacteria decompose glucose or starch via acetate fermentative metabolism as the rst step, and photosynthetic bacteria convert the resultant acetate to hydrogen in another reactor as the second stage. The hydrogen yield is increased two-fold in comparison to that using only dark-fermentation [59].

3.4.

Hydrogen production costs

Table 2 e Comparison of hydrogen yields were obtained by use of three different processes. Processes Hydrogen yield(wt%)
12.6 11.5 17.1

Hydrogen energy contents/biomass energy content

91 83 124

Pyrolysis catalytic reforming Gasication shift reaction Biomass steam except heat (theoretical maximum)

The major problem in utilization of hydrogen gas as a fuel is its unavailability in nature and the need for inexpensive production methods [8]. Steam methane reforming (SMR) is currently the most common and least expensive process for producing hydrogen from natural gas. In this method, natural gas feedstock costs generally contribute approximately 52e68% to the nal hydrogen price for larger plants, and 40% for smaller plants, with remaining expenses composed of capital charges [60]. Large-scale centralized power plants give way to smallscale distributed generation systems that operate nearer the point of use [61]. Hydrogen production costs from natural gas using SMR range from about 1.50 US$/kg at large-scale facilities (1.2 Gg/d) to about 3.75 US$/kg at a 500 kg/d facility (assumes 7

7420

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

Table 4 e Hydrogen costs used in long-term scenario modelling. Method Feedstock price
3e5 $/GJ 1e2 $/GJ 2e5 $/GJ 3e4 cents/kWh 4e5.5 cents/kWh 6e8 cents/kWh 12e20 cents/kWh 2.5e3.5 cents/kWh

Feedstock cost [$/GJ H2]

3.8e6.3 1.3e2.7 2.9e7.1 9.8e13.1 13.1e18.0 19.6e26.1 39.2e65.4 8.2e11.4

Other prod. cost [$/GJ H2]

1.2e2.7 4.7e6.3 5e6 5 5 5 5 5

Transport cost [$/GJ H2]

2 2 2e5 2e5 2e5 2e5 2e5 2

Refueling cost [$/GJ H2]

5e7 5e7 5e7 5e7 5e7 5e7 5e7 5e7

Total cost at fuel pump [$/GJ H2]

12e18 13e18 14e25 22e30 27e37 32e42 52e82 20e27

Natural gas with CCS Coal with CCS Biomass gasication Onshore wind Offshore wind Solar thermal elec. Solar PV Nuclear Source: Ref. [72].

US$/GJ natural gas price) [62]. The SMR process produces CO and CO2, the primary greenhouse gas. According to Muradov and Veziroglu [63], a typical SMR hydrogen plant with the capacity of approximately 1 million m3 of hydrogen per day produces 0.3e0.4 million standard cubic meters of CO2 per day, which is normally vented into the atmosphere. Several studies [64,65] showed that capturing CO2 adds about 25e30% to the cost of producing hydrogen by SMR. Hydrogen production by gasication and pyrolysis of biomass are not generally considered economically competitive with SMR processes. The price of hydrogen obtained by direct gasication of lignocellulosic biomass, however, is about three times higher than that for hydrogen produced by SMR [66]. According to Hamelinck and Faaij [67], the cost of producing hydrogen from biomass ranges from 10 to 14 US$/GJ, with a net higher heating value (HHV) energy efciency of 56e64%. It is believed that in the future biomass can become an important sustainable source of hydrogen. The future prospects for hydrogen economy or economic hydrogen production are the basic point of many articles [68]. Biomass residues are the cheapest feedstocks. Because of the low sulfur content of biomass, a sulfur removal system is not likely to be required. Several studies have shown that the cost of producing hydrogen from biomass is strongly dependent on the cost of the feedstock [69]. Hydrogen from biomass gasication is not expected to develop in the near term due to costs, lack of demonstrated technology and lack of widespread hydrogen market and infrastructure [70]. For a more longterm view of price competition, it is necessary to include both the variability in feedstock prices and the likely use of CO2 capture and storage (CCS) in fossil based processes [71]. As shown in Table 4, according to IEAs long-term scenario [72], hydrogen from biomass via gasication is expected to become quite competitive with the fossil routes including CCS, and the lowest cost of all the renewable routes in the next 40 years.

quantities of char and ash. Gasication generally involves pyrolysis as well as combustion to provide heat for the endothermic pyrolysis reactions [35]. Gasication is carried out at high temperatures in order to optimize the gas production. The resulting gas, known as producer gas, is a mixture of carbon monoxide, hydrogen and methane, together with carbon dioxide and nitrogen [73]. Most biomass gasication systems utilize air or oxygen in partial oxidation or combustion processes. At temperatures of approximately 875e1275 K, solid biomass undergoes thermal decomposition to form gas-phase products that typically include H2, CO, CO2, CH4, H2O, and other gaseous hydrocarbons (CHs) [74]. Gas composition of product from the biomass gasication depends heavily on the gasication process, the gasifying agent, and the feedstock composition [75]. Gasication of biomass is generally observed to follow the reaction: Biomass O2 (or H2O) / CO, CO2, H2O, H2, CH4 other CHs tar char ash

(1)

Assuming a gasication process using biomass as a feedstock, the rst step of the process is a thermo chemical decomposition of the cellulose, hemicelluloses and lignin compounds with production of char and volatiles [76]. Further the gasication of char and some other equilibrium reactions occur. Possible products obtained from gasication process are given in Fig. 2 [77].

4.2.

Hydrogen from biomass via gasication

4. Hydrogen production from biomass gasication

4.1. Principles of biomass gasication

The gasication of biomass is a thermal treatment, which results in a high production of gaseous products and small

Gasication of biomass has been identied as a possible system for producing renewable hydrogen, which is benecial to exploit biomass resources, to develop a highly efcient clean way for large-scale hydrogen production, and has less dependence on insecure fossil energy sources [41]. Most of the research spurred by this interest has been of economic technology in nature, based on gasier performance data acquired during system proof of conceptual tests. Less emphasis has been given to experimental investigation of hydrogen production via biomass gasication. Until now, all process equipment needed to produce hydrogen is well established in commercial use, except for the gasiers [78]. Biomass gasication can be considered as a form of pyrolysis, which takes place in higher temperatures and

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

7421

hydrogen production from biomass. Steam reforming and socalled dry or CO2 reforming occur according to the following reactions and are usually promoted by the use of catalysts. CnHm nH2O $ n CO (n m/2) H2 CnHm nCO2 $ (2n) CO (m/2) H2 (2) (3)

Fig. 2 e Products from gasication process.

produces a mixture of gases with H2 content ranging 6e6.5% [79]. The synthetic gas produced by the gasication of biomass is made up of H2, CO, CH4, N2, CO2, O2, and tar. When gasifying biomass, tar that is formed together with the synthetic gas is difcult to remove with a physical dust removal method [80]. The product distribution and gas composition depends on many factors including the gasication temperature and the reactor type [81]. The most important gasier types are xed bed (updraft or downdraft xed beds), uidized bed, and entrained ow gasiers. All these gasiers need to include signicant gas conditioning along with the removal of tars and inorganic impurities and the subsequent conversion of CO to H2 by water gas shift reaction. Table 5 shows typical gas composition data as obtained from commercial wood and charcoal downdraft gasiers operated on low to medium moisture content fuels [82]. Gasication technologies provide the opportunity to convert renewable biomass feedstocks into clean fuel gases or synthesis gases. The synthesis gas includes mainly hydrogen and carbon monoxide (H2 CO) which is also called as biosyngas [83]. Bio-syngas is a gas rich in CO and H2 obtained by gasication of biomass. Hydrogen production is the largest use of syngas. Biomass can be converted to bio-syngas by noncatalytic, catalytic, and steam gasication processes. Steam gasication is a promising technology for thermo chemical

Table 5 e Typical gas composition data as obtained from commercial wood and charcoal downdraft gasiers operated on low to medium moisture content fuels (wood 20%, charcoal 7%). Component
Wood gas Charcoal gas Source: Ref. [82].

H2 (%)

CO2 CH4 (%) (%)

CO (%)

N2 (%)

Heating value (MJ/m3)

5e5.9 4.5e5.6

12e20 9e15 2e3 17e22 50e54 4e10 1e3 0e2 28e32 55e65

Modeling of biomass steam gasication to synthesis gas is a challenge because of the variability (composition, structure, reactivity, physical properties, etc.) of the raw material and because of the severe conditions (temperature, residence time, heating rate, etc.) required [84]. The yield of H2 from steam gasication increases with increasing water-to-sample (W/S) ratio [85]. The yields of hydrogen from the pyrolysis and the steam gasication increase with increasing of temperature. In general, the gasication temperature is higher than that of pyrolysis and the yield of hydrogen from the gasication is higher than that of the pyrolysis [86]. Demirbas [87] investigated the yields of hydrogen from pyrolysis and steam gasication of corncob at different temperatures. The yield of hydrogen from conventional pyrolysis of corncob increased from 33 to 40% with increasing of temperature from 775 to 1025 K. The yield of hydrogen from steam gasication of corncob increased from 29 to 45% for (W/S) 1 and from 29 to 47% for (W/S) 2 with increasing of temperature from 975 to 1225 K. The effect of catalyst on gasication products is very important. The use of the catalyst did not affect the gas yields, but the composition of the gases was strongly inuenced. The content of H2 and CO2 increased, while that of CO decreased; a drastic reduction in the content of organic compounds could also be observed. Because the char yields remained almost constant compared to an equivalent no catalytic thermal run, the increase in the content of hydrogen was probably due to the inuence of the catalyst on the water gas shift reaction [85]. Dolomite, Ni-based catalysts and alkaline metal oxides are widely used as gasication catalysts [88]. Mg-promoted catalysts showed a greater difculty for Ni precursors reduction besides different probe molecules (H2 and CO) adsorbed states. In the conversion of cyclohexane, Mg inhibited the formation of hydrogenolysis products. Nonetheless, the presence of Ca did not inuence the metallic phase. The impregnated Ni/MgO-catalyst performed better than the other types [79]. Hydrogen production from biomass has major challenges. There are no completed technology demonstrations. The yield of hydrogen is low from biomass since the hydrogen content in biomass is low to begin with (approximately 6% versus 25% for methane) and the energy content is also low due to high oxygen content (about 40 wt% of biomass). Since over half of the hydrogen from biomass comes from spitting water in the steam reforming reaction, the energy content of the feedstock is an inherent limitation of the process [44,89]. The yield of hydrogen as a function of oxygen content is shown in Fig. 3. However, the cost for growing, harvesting and transporting biomass is high. Thus, even with reasonable energy efciencies, it is not presently economically competitive with natural gas steam reforming for stand-alone hydrogen without the advantage of high-value co-products. Additionally, as with all sources of hydrogen, production from biomass will require

7422

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

Table 6 e Share of individual primary energy sources in meeting nal energy needs (%). Source of energy
Fossil fuels Nuclear energy Hydrogen from solar energy Electricity from solar energy Heat from solar energy Energy from solar energy Hydrogen Source: Ref. [100].

1998
88 10 e e e 2 e

2025
62 2 7 11 18 25 11

2050
29 2 31 16 22 35 34

Fig. 3 e Theoretical yield of H2 as a function of the oxygen content in the feed. Source: Ref. [44].

appropriate hydrogen storage, transport infrastructure and utilization systems to be developed and deployed [44].

future perspectives of fuel cells [94]. The scenario illustrates the key role of hydrogen in a long-term transition towards a clean and sustainable energy future. According to this scenario, biomass gasication will become a dominant technology in the future (Fig. 4).

4.3. Role of biomass gasication in the future hydrogen supply

Today, hydrogen is mainly produced from natural gas via steam methane reforming, and although this process can sustain an initial foray into the hydrogen economy, it represents only a modest reduction in vehicle emissions as compared to emissions from current hybrid vehicles, and ultimately only exchanges oil imports for natural gas imports [90]. It is clearly not sustainable. Biomass has been recognized as a major world renewable energy source to supplement declining fossil fuel resources [91,92]. It will play an important role in the future global energy infrastructure for the generation of power and heat, but also for the production of chemicals and fuels. The dominant biomass conversion technology will be gasication, as the gases from biomass gasication are intermediates in the high-efcient power production or the synthesis from chemicals and fuels [93]. Biomass gasication offers the earliest and most economical route for the production of renewable hydrogen. IIASAs Environmentally Compatible Energy Strategies (ECS) project has developed a long-term hydrogen-based scenario (B1-H2) of the global energy system to examine the

5. Role of hydrogen in the future global energy supply

Energy demand has grown strongly and will continue to increase, particularly in developing countries where energy is needed for economic growth and poverty alleviation. In the beginning of this new century, the rational use of energy becomes a keyword for the world sustainable development both in developed and developing countries [95]. Projected world primary energy demand by 2050 is expected to be in the range of 600e1000 EJ (compared to about 500 EJ in 2008) [96]. At the present time primary energy sources are dominated by fossil fuels, with nearly 80% of global energy demand supplied from crude oil, natural gas, and coal [97]. Petroleum-based fuels are limited reserves concentrated in certain regions of the world. These sources are on the verge of reaching their peak production. Known petroleum reserves are estimated to be depleted in less than 50 years at the present rate of consumption [98]. As supplies of fossil fuels dwindle and concerns about continued contributions of additional carbon dioxide to the atmosphere intensify, there is an increasing need for new sources of energy from renewable carbon-neutral sources with minimal negative environmental impact [99]. Renewable energy is expected to play a major role in the global future energy provision. Hydrogen and fuel cells are often considered as a key technology for future sustainable energy supply. Renewable shares of 36% (2025) and 69% (2050) on the total energy

Table 7 e Percentage point shares of alternative fuels in total automotive fuel consumption in the EU under the optimistic development scenario of the European Commission. Year Fig. 4 e Global hydrogen supply mix for the period 2000e2100 in the B1-H2 scenario. Steam reforming of natural gas and gasication of biomass are the dominant technologies. Source: Ref. [61].
2010 2015 2020

Biofuel
6 7 8

Natural gas
2 5 10

Hydrogen
e 2 5

Total
8 14 23

Source: Ref. [105].

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

7423

Fig. 5 e Shares of alternative fuels compared to the total automotive fuel consumption in the world. Source: Ref. [107].

demand will lead to hydrogen shares of 11% in 2025 and 34% in 2050 [100]. The share of individual primary energy sources in meeting nal energy needs are given in Table 6. Carbon dioxide is main greenhouse gas associated with global warning, is produced in all combustion processes involving fossil fuels as well in other industrial processes such as cement production and sweetening of natural gas [101]. One-fth of global carbon dioxide emissions are created by the transport sector, which accounts for some 60% of global oil consumption [102]. For that reason, alternate transportation fuels, such as ethanol, biodiesel, and hydrogen, will play an important role in the worlds future. Due to the increasing mobility of people and goods, the transport sector accounts for more than 30% of nal energy consumption in the European Union (EU) and is expanding [103]. The European Commission White Paper [104] calls for dependence on oil in the transport sector to be reduced by using alternative fuels such as biofuels. An increasing use of biofuels for transport is emerging as an important policy strategy to substitute petroleum-based fuels [103]. Regarding fuel substitution, the Commission stakes mainly on biofuels, natural gas (CNG), and hydrogen/fuel cells and envisages the following scenario, dubbed by the Commission herself the optimistic development scenario(Table 7) [105]. As is evidenced by several funded programs from many national government agencies all over the world, hydrogen is being promoted as the fuel for the future [106]. Fig. 5 shows the shares of alternative fuels compared to the total automotive fuel consumption in the world as a futuristic view [107].

exchanges oil imports for natural gas imports. It is clearly not sustainable. Hydrogen produced through a range of renewable primary energy sources such as wind, biomass, and solar energy is ideal for gradually replacing fossil fuels. The use of renewable biomass as a major feedstock for hydrogen production has received considerable attention in recent years. Hydrogen can be generated from biomass, but this technology urgently needs further development. The production of hydrogen from biomass is already economically competitive today. Hydrogen production from biomass has major challenges. There are no completed technology demonstrations. It is believed that in the future biomass can become an important sustainable source of hydrogen. Due to its environmental merits, the share of hydrogen from biomass in the automotive fuel market will grow fast in the next decade. Gasication of biomass has been identied as a possible system for producing renewable hydrogen, which is benecial to exploit biomass resources, to develop a highly efcient clean way for large-scale hydrogen production, and has less dependence on insecure fossil energy sources. Steam reforming of natural gas and gasication of biomass will become the dominant technologies by the end of the 21st century.

references

6.

Conclusion

Today, hydrogen is mainly produced from natural gas via steam methane reforming, and although this process can sustain an initial foray into the hydrogen economy, it represents only a modest reduction in vehicle emissions as compared to emissions from current hybrid vehicles, and ultimately only

[1] Loppacher LJ, Kerr WA. Can biofuels become a global industry?: government policies and trade constraints. Energy Politics 2005;5:7e27. [2] Balat M. Bioethanol as a vehicular fuel: a critical review. Energy Sources Part A 2009;31:1242e55. [3] Demirbas MF. Bio-oils from corn stover via supercritical water liquefaction. Energy Educ Sci Technol Part A 2009;23:97e104. [4] Demirbas A, Dincer K. Sustainable green diesel: a futuristic view. Energy Sources Part A 2008;30:1233e41. [5] Demirbas A. The importance of bioethanol and biodiesel from biomass. Energy Sources Part B 2008;3:177e85. [6] Veziroglu TN, Sahin S. 21st centurys energy: hydrogen energy system. Energy Convers Manage 2008;49:1820e31. [7] Balat M. Potential importance of hydrogen as a future solution to environmental and transportation problems. Int J Hydrogen Energ 2008;33:4013e29. [8] Kapdan IK, Kargi F. Bio-hydrogen production from waste materials. Enzym Micro Tech 2006;38:569e82. [9] Cherry RS. A hydrogen utopia. Int J Hydrogen Energ 2004;29: 125e9. [10] Gemici Z, Ulusarslan T, Teke I. Currency of district cooling systems and alternative energy sources. Energy Educ Sci Technol Part A 2009;23:31e53. [11] Shakya BD, Aye L, Musgrave P. Technical feasibility and nancial analysis of hybrid windephotovoltaic system with hydrogen storage for cooma. Int J Hydrogen Energ 2005;30: 9e20. [12] Mohan SV, Bhaskar YV, Sarma PN. Biohydrogen production from chemical wastewater treatment in biolm congured reactor operated in periodic discontinuous batch mode by selectively enriched anaerobic mixed consortia. Water Res 2007;41:2652e64. [13] Das D, Khanna N, Veziroglu TN. Recent developments in biological hydrogen production processes. Chem Ind Chem Eng Q 2008;14:57e67. [14] Yolcular S. Hydrogen production for energy use in European Union countries and Turkey. Energy Sources Part A 2009;31: 1329e37.

7424

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

[15] Larsen H, Feidenhansl R, Petersen LS. Hydrogen and its competitors, Ris energy Report 3. Roskilde, Denmark: Ris National Laboratory; November 2004. [16] Demirbas A. Biohydrogen for future engine fuel demands. London: Springer; 2009. [17] Kraus T. Hydrogen fuel-an economically viable future for the transportation industry. Duke J Econ 2007;19:1e39. Spring. [18] Konieczny A, Mondal K, Wiltowski T, Dydo P. Catalyst development for thermocatalytic decomposition of methane to hydrogen. Int J Hydrogen Energ 2008;33:264e72. [19] Balat M. Hydrogen in fueled systems and the Signicance of hydrogen in vehicular transportation. Energy Sources Part B 2007;2:49e61. [20] Yaman S. Pyrolysis of biomass to produce fuels and chemical feedstocks. Energy Convers Manage 2004;45:651e71. [21] Demirbas A. Pyrolysis of biomass for fuels and chemicals. Energy Sources Part A 2009;31:1028e37. [22] Balat M. Gasication of biomass to produce gaseous products. Energy Sources Part A 2009;31:516e26. [23] Abella L, Nanbu S, Fukuda K. A theoretical study on levoglucosan pyrolysis reactions yielding aldehydes and a ketone in biomass, vol. 67. Memoirs of Faculty of Engineering, Kyushu University; 2007. pp. 67e74. [24] Demirbas A. Products from lignocellulosic materials via degradation processes. Energy Sources Part A 2008;30: 27e37. [25] Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/ biomass for bio-oil: a critical review. Energy Fuels 2006;20: 848e89. [26] Feldman D, Banu D, Natansohn A, Wang J. Structureproperties relations of thermally cured epoxy-lignin polyblends. J App Polym Sci 1991;42:1537e50. [27] Caputo AC, Palumbo M, Pelagagge PM, Scacchia F. Economics of biomass energy utilization in combustion and gasication plants: effects of logistic variables. Biomass Bioenerg 2005;28:35e51. [28] Karekezi S., Lata K., Coelho S.T.. Traditional biomass energy-improving its use and moving to modern energy use, in: processing of Secretariat of the International Conference for Renewable Energies, Bonn, June 1e4, 2004. [29] Jekayinfa SO, Scholz V. Potential availability of energetically usable crop residues in Nigeria. Energy Sources Part A 2009; 31:687e97. [30] Ladanai S, Vinterback J. Global potential of sustainable biomass for energy, report 013. Uppsala: Department of Energy and Technology, Swedish University of Agricultural Sciences; 2009. [31] Charles MB, Ryan R, Oloruntoba R, von der Heidt T, Ryan N. The EUeAfrica energy partnership: towards a mutually benecial renewable transport energy alliance. Energy Policy 2009;37:5546e56. [32] Hoogwijk M, Faaij A, Eickhout B, de Vries B, Turkenburg W. Potential of biomass energy out to 2100, for four IPCC SRES land-use scenarios. Biomass Bioenerg 2005;29:225e57. [33] Caglar A. Valorization of tea wastes by pyrolysis. Energy Educ Sci Technol Part A 2009;23:135e44. [34] Bhuiyan MNA, Ota M, Murakami K, Yoshida H. Pyrolysis kinetics of newspaper and its gasication. Energy Sourcec Part A 2010;32:108e18. [35] Demirbas A. Liquefaction of biomass using glycerol. Energy Sources Part A 2008;30:1120e6. [36] Sener U, Genel Y, Saka C, Kilicel F, Kucuk MM. Supercritical uid extraction of cotton stalks. Energy Sources Part A 2010; 32:20e5. [37] Demirbas A. Biofuels from agricultural biomass. Energy Sources Part A 2009;31:1573e82. [38] Bakis R. Alternative electricity generation opportunities. Energy Sources Part A 2008;30:141e8.

[39] Demirbas A. Biohydrogen generation from organic wastes. Energy Sources Part A 2008;30:475e85. [40] National Research Council (U.S.). The hydrogen economy: opportunities, costs, barriers, and R&D needs. Washington, DC: National Academies Press; February 2004. [41] Balat M. Hydrogen-rich gas production from biomass via pyrolysis and gasication processes and effects of catalyst on hydrogen yield. Energy Sources Part A 2008; 30:552e64. [42] Antonopoulou G, Gavala HN, Skiadas IV, Angelopoulos K, Lyberatos G. Biofuels generation from sweet sorghum: fermentative hydrogen production and anaerobic digestion of the remaining biomass. Bioresour Technol 2008;99:110e9. [43] Ni M, Leung MKH, Sumathy K, Leung DYC. Potential of renewable hydrogen production for energy supply in Hong Kong. Int J Hydrogen Energ 2006;31:1401e12. [44] Milne TA, Elam CC, Evans RJ. Hydrogen from biomass- state of the art and research challenges, Report for IEA, IEA/H2/ TR-02/001. Golden, CO: National Renewable Energy Laboratory; 2002. [45] Patel A.G., Maheshwari N.K., Vijayan P.K., Sinha R.K.. A study on sulfur-iodine (S-I) thermochemical water splitting process for hydrogen production from nuclear heat, in: processing of Sixteenth Annual Conference of Indian Nuclear Society, Science behind Nuclear Technology, Mumbai, India, November 15e18, 2005. [46] Demirbas A. Yields of hydrogen of gaseous products via pyrolysis from selected biomass samples. Fuel 2001;80: 1885e91. [47] Wang D, Czernik S, Montane D, Mann M, Chornet E. Biomass to hydrogen via fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its fractions. Ind Eng Chem Res 1997;36:1507e18. [48] Yan Q, Guo L, Lu Y. Thermodynamic analysis of hydrogen production from biomass gasication in supercritical water. Energy Convers Manage 2006;47:1515e28. [49] Swami SM, Chaudhari V, Kim DS, Sim SJ, Abraham MA. Production of hydrogen from glucose as a biomass simulant: integrated biological and thermochemical approach. Ind Eng Chem Res 2008;47:3645e51. [50] Sricharoenchaikul V, Marukatat C., Atong T.. Fuel production from physic nut (Jatropha Curcas L.) waste by xed-bed pyrolysis process. In: Processing of 3rd Conference on Energy Network of Thailand, ENETT2550072, Bangkok, Thailand, May 23e25, 2007. [51] Das D, Veziroglu TN. Hydrogen production by biological processes: a survey of literature. Int J Hydrogen Energ 2001; 26:13e28. [52] Nandi R, Sengupta S. Microbial production of hydrogendan overview. Crit Rev Microbiol 1998;24:61e84. [53] Cheong DY, Hansen CL. Bacterial stress enrichment enhances anaerobic hydrogen production in cattle manure sludge. Appl Microbiol Biotechnol 2006;72:635e43. [54] Ren N, Li J, Li B, Wang Y, Liu S. Biohydrogen production from molasses by anaerobic fermentation with a pilotscale bioreactor system. Int J Hydrogen Energ 2006;31: 2147e57. [55] O-Thong S, Prasertsan P, Karakashev D, Angelidaki I. Thermophilic fermentative hydrogen production by the newly isolated Thermoanaerobacterium thermosaccharolyticum PSU-2. Int J Hydrogen Energ 2008;33:1204e14. [56] de vrije T, Bakker RR, Budde MAW, Lai MH, Mars AE, Claassen PAM. Efcient hydrogen production from the lignocellulosic energy crop Miscanthus by the extreme thermophilic bacteria Caldicellulosiruptor saccharolyticus and Thermotoga neapolitana. Biotechnol Biofuels 2009;2:12.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

7425

[57] Zheng H., OSullivan C., Mereddy R., Zeng R.J., Duke M., Clarke W.. Production of bio-hydrogen using a membrane anaerobic reactor: limitations due to diffusion. In: Proceedings of the Environmental Research Event 2009, Noosa Heads, Queensland, Australia, May 10-13, 2009. [58] Kotay SM, Das D. Biohydrogen as a renewable energy resourcedprospects and potentials. Int J Hydrogen Energ 2008;33:258e63. [59] Tao Y, Chen Y, Wu Y, He Y, Zhou Z. High hydrogen yield from a two-step process of dark- and photo-fermentation of sucrose. Int J Hydrogen Energ 2007;32:200e6. [60] Roan V, Betts D, Twining A, Dinh K, Wassink P, Simmons T. Investigation of the feasibility of coal-based methanol for application in transportation fuel cell systems. Florida, USA: Georgetown University Advanced Vehicle Development Program; April 2004. Final Report. [61] Barreto L, Makihira A, Riahi K. The hydrogen economy in the 21st century: a sustainable development scenario. Int J Hydrogen Energ 2003;28:267e84. [62] Williams R.B., Kornbluth K., Erickson P.A., Jenkins B.M., Gildart M.C.. Estimates of hydrogen production potential and costs from California Landll Gas. In: proceedings of 15th European Biomass Conference and Exhibition, Berlin, Germany, May 7e11, 2007. [63] Muradov NZ, Veziroglu TN. From hydrocarbon to hydrogenecarbon to hydrogen economy. Int J Hydrogen Energ 2005;30:225e37. [64] Muradov N. Hydrogen from fossil fuels without CO2 emissions. In: Padro CEG, Lau F, editors. Advances in hydrogen energy. US: Springer; 2002. p. 1e16. [65] Tseng P, Lee J, Friley P. Hydrogen economy: opportunities and challenges. Energy 2005;30:2703e20. [66] Spath P.L., Mann M.K., Amos W.A., Update of hydrogen from biomass: determination of the delivered cost of hydrogen, NREL Milestone Report, NREL/MP-510e33112, Golden, Colorado, December 2003. [67] Hamelinck CN, Faaij APC. Future prospects for production of methanol and hydrogen from biomass. J Power Sources 2002;111:1e22. [68] Veziroglu TN. Dawn of the hydrogen age. Int J Hydrogen Energ 1998;23:1077e8. [69] Balat M, Balat M. Political, economic and environmental impacts of biomass-based hydrogen. Int J Hydrogen Energ 2009;34:3589e603. [70] Williams R, Parker N, Yang C, Ogden J, Jenkins B. H2 Production via biomass gasication, prepared for public interest energy research (PIER) program. Davis, CA: California Energy Commission; July 2007. [71] International Energy Agency, Prospects for Hydrogen from Biomass, IEA Hydrogen Implementing Agreement, Annex 16, Subtask B, Final Report, June 2006. [72] Gielen D, Simbolotti G. Prospects for hydrogen and fuel cells. In: IEA energy technology analysis series, vol. 2. Paris: OECD/IEA; 2005. [73] Demirbas B. Biomass business and operating. Energy Educ Sci Technol Part A 2010;26:37e47. [74] Balat H. Prospects of biofuels for a sustainable energy future: a critical assessment. Energy Educ Sci Technol Part A 2010;24:85e111. [75] Balat M. Mechanisms of thermochemical biomass conversion processes. Part 2: reactions of gasication. Energy Sources Part A 2008;30:636e48. [76] Demirbas MF. Bioreneries for biofuel upgrading: a critical review. Appl Energy 2009;86:S151e61. [77] Balat M, Balat M, Krtay E, Balat H. Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 2: gasication systems. Energy Convers Manage 2009; 50:3158e68.

[78] Kong L, Li G, Zhang B, He W, Wang H. Hydrogen production from biomass wastes by hydrothermal gasication. Energy Sources Part A 2008;30:1166e78. [79] Demirbas A. Hydrogen production from carbonaceous solid wastes by steam reforming. Energy Sources Part A 2008;30: 924e31. [80] Yoon SJ, Choi YC, Lee JG. Hydrogen production from biomass tar by catalytic steam reforming. Energy Convers Manage 2010;51:42e7. [81] Stevens D.J. Hot Gas Conditioning: recent Progress with Larger-Scale Biomass Gasication Systems, NREL Subcontractor Report: NREL/SR-510e29952, Golden, Colorado, August 2001. [82] Stassen HEM, Knoef HAM. Small scale gasication systems. The Netherlands: Biomass Technology Group, University of Twente; 1993. [83] Demirbas AH. Biofuels for future transportation necessity. Energy Educ Sci Technol Part A 2010;26:13e23. [84] Dupont C, Boissonnet G, Seiler JM, Gauthier P, Schweich D. Study about the kinetic processes of biomass steam gasication. Fuel 2007;86:32e40. [85] Maschio G, Lucchesi A, Stoppato G. Production of syngas from biomass. Bioresour Technol 1994;48:119e26. [86] Balat M. Possible methods for hydrogen production. Energy Sources Part A 2009;31:39e50. [87] Demirbas MF. Hydrogen from various biomass species via pyrolysis and steam gasication processes. Energy Sources Part A 2006;28:245e52. [88] Ni M, Leung DYC, Leung MKH, Sumathy K. An overview of hydrogen production from biomass. Fuel Process Tech 2006; 87:461e72. [89] Kalinci Y, Hepbasli A, Dincer I. Biomass-based hydrogen production: a review and analysis. Int J Hydrogen Energ 2009;34:8799e817. [90] Turner JA. Sustainable hydrogen production. Inform 2004; 305:971e4. [91] Kan A. General characteristics of waste management: a review. Energy Educ Sci Technol Part A 2009;23:55e69. [92] Unal H, Alibas K. Agricultural residues as biomass energy. Energy Sources Part B 2007;2:123e240. [93] Boerrigter H, Rauch R. Review of applications of gases from biomass gasication. In: Knoef HAM, editor. Handbook biomass gasication. The Netherlands: Biomass Technology Group (BTG); 2005. p. 211e30. [94] Barreto L, Makihira A, Riahi K. Medium and long-term demand and supply prospects for fuel cells: the hydrogen economy and perspectives for the 21st century. Final Report on the TEPCO-IIASA Collaborative Study, IIASA Contract No 00e101. Laxenburg, Austria: International Institute for Applied Systems Analysis; 2002. [95] Marechal F, Favrat D, Jochem E. Energy in the perspective of the sustainable development: the 2000 W society challenge. Res Conser Recycling 2005;44:245e62. [96] International Energy Agency. Bioenergy e a sustainable and reliable energy source: a review of status and prospects. Paris: IEA Bioenergy, OECD/IEA; December 2009. [97] Evans RL. Fueling our future: an introduction to sustainable energy. Cambridge: Cambridge University Press; April 19, 2007. [98] Sheehan J, Cambreco V, Dufeld J, Garboski M, Shapouri H, An overview of biodiesel and petroleum diesel life cycles, A report by US Department of Agriculture and Energy, Washington, DC, 1998. [99] Lovley DR. Microbial fuel cells: novel microbial physiologies and engineering approaches. Curr Opin Biotechnol 2006;17: 327e32.

7426

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 1 6 e7 4 2 6

[100] Rohland B, Nitsch J, Wendt H. Hydrogen and fuel cells d the clean energy system. J Power Sourc 1992;37:271e7. [101] Keskin A, Emiroglu AO. Catalytic reduction techniques for post-combustion diesel engine exhaust emissions. Energy Educ Sci Technol Part A 2010;25:87e103. [102] Balat M, Balat H. Recent trends in global production and utilization of bio-ethanol fuel. Appl Energ 2009;86:2273e82. [103] Malca J, Freire F. Renewability and life-cycle energy efciency of bioethanol and bio-ethyl tertiary butyl ether (bioETBE): assessing the implications of allocation. Energy 2006;31:3362e80.

[104] European Commission, European transport policy for 2010: time to decide, White Paper, COM (2001)370, Brussels, September 2001. [105] Jansen JC. Policy support for renewable energy in the European Union. Energy Research Centre of the Netherlands. Available from: www.ecn.nl/docs/library/ report/2003/C03113.pdf; 2003 [accessed on March 2010]. [106] Saxena SK. Hydrogen production by chemically reacting species. Int J Hydrogen Energ 2003;28:49e53. [107] Demirbas A. Global renewable energy projections. Energy Sources Part B 2009;4:212e24.